Tricyclic ketals as herbicides



United States Patent 3,419,380 TRICYCLIC KETALS AS HERBICIDES Paul E.Hoch, Youngstown, and George B. Stratton,

Lewiston, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls,N.Y., a corporation of New York No Drawing. Continuation-impart ofapplication Ser. N 0. 413,947, Nov. 25, 1964. This application Nov. 26,1965, Ser. No. 510,025

11 Claims. (CI. 71-88) ABSTRACT OF THE DISCLOSURE A method forcontrolling plant growth, utilizing a tricyclic ketal of the formula inwhich the Xs are hydrogen, halogen or an organic radical; Y is anucleophilic radical; and the Rs represent an organic radical.

This is a continuation-in-part of copending application Ser. No.413,947, filed Nov. 25, 1964, now US. Patent No. 3,346,596, which is acontinuation-in-part of application Ser. No. 327,519, tiled Dec. 2,1963, now US. Patent No. 3,331,860.

This invention relates to the methods for utilizing certain tricyclicketals in the control of pests, the regulation of plant growth, andother biological methods. The invention relates to compounds having theformula wherein X and X are independently selected from the groupconsisting of hydrogen, halogen, alkyl, alkenyl, halogenated alkyl andhalogenated alkenyl;

X and X are independently selected from the group consisting ofhydrogen, halogen, alkoxy, alkyl, alkenyl, halogenated alkyl, andhalogenated alkenyl, at least two of X X X and X being halogen;

X is selected from the group consisting of hydrogen,

halogen and alkoxy;

Y is a nucleophilic radical;

R and R are independently selected from the group consisting ofhydrogen, hydrocarbyl, halogen-substituted hydrocarbyl, and carboxyl;

R and R are independently selected from the group consisting ofhydrogen, hydrocarbyl, halogen-substituted hydrocarbyl,hydroxy-substituted alkyl, alkoxysubstituted alkyl, andhy'droXy-substituted alkoxyalkyl; and

R and R are cycloalkyl when -R and R join to form a ring; provided thatat least one of R and R can be hydroxy-substituted alkyl when Y is oneof halogen, hydroxy, hydrocarbyloxy, mercapto, substitutedbydrocarbyloxy and substituted hydrocarbyl mercapto.

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The hydrocarbyl radicals are monovalent radicals derivable from ahydrocarbon by the removal of one hydrogen atom. Typical hydrocarbyl,radicals are alkyl, alkenyl, alkynyl, alkadienyl, aryl, cycloalkyl andthe like, defined with greater particularly herein.

Illustrative examples of the alkyl substituents, which usually containfrom 1 to about 18 carbon atoms, and preferably from 1 to about 6 carbonatoms, are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amylhexyl, cyclohexyl, heptyl, octyl, nonyl, dodecyl, pentadecyl, stearyl,octadecyl, and the like, said alkyl group being a monovalent radicalderivable from an aliphatic hydrocarbon by the removal of one hydrogenatom. The alkylene radicals can be similarly described, except that theyare divalent radicals derivable from an aliphatic hydrocarbon by theremoval of two hydrogen atoms, such as methylene; ethylene and the like.The alkyl radical can be substituted by halogen, such as chlorine,bromine, or fluorine, as in chloromethyl, diohloromethyl,trichloromethyl, trifluoromethyl, bromoethyl, chloroethyl, fluoropropyl,hexachl'oroisopropyl, chlorobutyl, bromobutyl, chlorocyclohexyl,chloropropyl, bromooctyl, chlorooctyl, chlorodecyl, ohlorododecyl,bromododecyl, bromopentadecyl, and the like.

Among the alkenyl, alkynyl and alkadienyl substituents which usuallycontain from 1 to about 18 carbon atoms, and preferably from 1 to about6 carbon atoms, are vinyl, ethynyl, allyl, propynyl, butenyl,butadienyl, methyl butadienyl, hexenyl, octenyl, dodecenyl, and the likesaid alkenyl group being a radical derivable from an alkene by theremoval of one hydrogen atom. The alkenyl radical can be substituted byhalogen, such as chlorine, bromine or fluorine, as in triehlorovinyl,2-chloroallyl, 2, 3-difiuorobutenyl, 2,3-dichlorododecenyl,2-bromoallyl, and the like.

Typical aryl substitutents, including aralkyl and alkaryl groups, whichusually contain from 6 to about 10 carbon atoms, are phenyl, benzyl,tolyl, phenylethyl, x-ylyl, naphthyl, hexylphenyl, and the like, saidaryl group being a monovalent radical derivable from an aromatichydrocarbon by the removal of one hydrogen atom. The aryl radicals canbe substituted by halogen, such as chlorine, bromine and fluorine, as inp-chlorophenyl, p-brombphenyl, p-fluorophenyl and the like.

Typical cycloalkyl substituents, which usually contain from three toabout twelve carbon atoms, are cyclohexyl, cyclopropyl, cyclopentyl,cycloheptyl, cyclooctyl, and the like, said cycloalkyl group being amonovalent radical derivabe from an alicyclic hydrocarbon by the removalof one hydrogen atom. The cycloalkyl radicals can be substituted byhalogen, e.g., chlorine, bromine and fluorine, as in chlorocyclohexyl,bromocyclopentyl, fluorocyclohexyl, and the like.

The substituting halogen atoms which are useful include chlorine,bromine and fluorine. The halogenated alkyl, aryl, cycloalkyl or alkenylradicals can bear from one up to a number, corresponding toperhaogenation, i.e., all hydrogens replaced with halogen atoms.

Typical nucleophilic radicals, as the term is employed herein, arehalogen, hydroxy, hydrocarbyloxy, mercapto, cyano, thiocyano, carboxy,azido, hydrocarbylmercapto, hydroxy-substituted hydrocarbyloxy,hydroXy-substituted hydrocarbylrnercapto, mercapto-substitutedhydrocarbyloxy, mercapto-substituted hydrocarbylmercapto,hydrocarbyloxy-substituted hydrocarbyloxy, hydrocarbyloxysubstitutedhydrocarbylmercapto, hydrocarbylthiohydrocarbylmercapto, andhydrocarbylthiohydrocarbyloxy, wherein the hydrocarbyl groups are asdefined hereinbefore, and can be halogen-substituted, as desired.

The preferred compounds of the invention are those wherein the halogensubstitutents are chlorine or bromine,

in which R and R are hydrogen, R is selected from1,2,4,5,5-pentachlorocyclopentadiene; hydrogen, chloro-substituted loweralkyl, hydroxy-subtetrachlorocyclopentadiene; stituted lower alkyl, andcarboxy; and R is selected froml,2,3,4-tetrachloro-5,S-dibromocyclopentadiene; hydrogen,chloro-substituted lower alkyl, and lower al-1,2,3,4-tetrachloro-5,S-difluorocyclopentadiene; koxy-substituted loweralkyl. Even more preferred are 51,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene; such compounds whereinthe halogen is chlorine. The1,3,4-trichloro-2,5,S-trimethoxycyclopentadiene; preferred nucleophilicradicals are chlorine, alkoxy,aryltrichloromethylpentachlorocyclopentadiene; oxy, hydroxy, cyano,carboxy and hydroxy-substitutedtrichlorovinylpentachlorocyclopentadiene; alkoxy. Lower alkyl radicalshave one to six carbon butenylpentachlorocyclopentadiene; atomsand thelike. The usual halogen substitutents are chlorine,

The compounds of the lnventlon are P p In a fluorine, bromine andmixtures thereof, preferably chloseries of reactions starting withselected bicyclic alcohols i S i bl l l are, f r example, 2 1 1.

as disclosed in application 413,947- These cohol; cinnamyl alcohol;l-carboxy-S-hydroxy propene-l; cqhols are P p e by l'eactlng the pp p2-butene-L4-diol; 3-hexene-2,5diol; 8-hexadecene-7,l0- strtutedcyclopentadiene and unsaturated alcohol as reprediol;1,4-cyclohexyl-2-butene-1,4-diol; 3,4-dihydroxy-2 Sented y thfifollowing quation. butene; 3-hydroxycyclopentene-1;3-hydroxycyclohexenewherem 1 and the like. Compounds that are readilyconverti- X and X are independently selected from the group ble toalcohols in the reaction process are also useful, such consisting ofhydrogen, halogen, alkyl and alkenyl; as 3,4-epoxy-1-butene and3,4-epoxy-l-hexane.

X and X are independently selected from the group The preparation of thecompounds of the invention is consisting of hydrogen, halogen, alkoxy,alkyl, and illustrated in the following equations wherein thereacalkenyl, at least two of X X X and X being 3 tion steps aredesignated by the letters A through H, halogen; but is not intended tobe limited thereby.

H 01 c1 01 H 01 H H (:1. H 01 2 A 2 0 C1 D 01 H 31 c1 ca es 15 H E HZ HCH Cl EC 91 H 01 2 61 H 1500c u H 5 X and X are independently selectedfrom the group The preparation of the compounds of the inventionconsrstmg of hydrogen, halogen and alkoxy, at least is furtherillustrated in the following examples which one of X and X beinghalogen; shows the preparation of specific compounds. All parts R and Rare rndependently selected from the group 0 are by weight, all analysesare given in percentages by cqflslstlng of y g y y and Y yweight, andtemperatures are given in degrees centigrade, strtuted alkyl; unlessindicated otherwise, in all the succeeding examples.

R and R are independently selected from the group consisting ofhydrogen, hydrocarlbyl hydroxy sub Example 1.Preparat1on of4-ethoxy-5,6,7,7,8-penta Stituted alkyl, alkoxy substituted alkyl andhydroxy chloro-3-oxatricyclo[4.2.1.0 ]nonane (Reaction A) substitutedalkoxyalkyl, and A solution of sodium ethoxide was prepared by adding Rand R can join to form a cycloalkyl group, gen- 92 parts of sodium metalto 3,925 parts of absolute etherally of 5 to 6 carbon atoms. anol. Tothis solution was added, with stirring at 74 de- The halogen,hydrocarbyl, alkyl, and alkenyl radicals grees Centigradfi, a Solutionof 331 Parts Of 5 1 are the same as those described hereinbefore. Theprephexachloro-Z-hydroxymethylbicyclo(2.2.l) S-heptene in aration ofsuch alcohols is described in detail in US. 785 parts of absoluteethanol. Addition was made portion- Patent 3,007,958. Suitablecyclopentadiene include, for wise over one hour. The suspension wasstirred at reflux example, for two hours after addition of the reactantswas com- 1,2,3,4,5,5-hexachlor0cyclopentadiene; pleted. Four thousandparts of water were added to the 1,2,3,4,5-pentachlorocyclopentadiene;75 reaction at completion, and the pH was adjusted with hydrochloricacid to 7.0. The solid that precipitated was collected on a filter,washed several times with water and dried under vacuum at 50 degreescentigrade overnight to a constant weight of 332 parts.Recrystallization from n-heptane and a treatment with activated charcoalyielded 325 parts of product, having a melting point of 110 to 111.5degrees centigrade. Product analysis was:

Calculated for C H O Cl Cl, 52.1; C, 35.3; H, 3.24. Found: Cl, 52.0; C,35.4; H, 3.36.

4 methoxy 5,6,7,7,8 pentachloro 3 oxatricyclo- [4.2.l.O ]nonane isprepared in the same manner using methanol in place of ethanol.

Example 2.Preparation of 4-(2,4-dichlorophenoxy)- 5,6,7,7,8pentachloro-3-oxatricyclo[4.2.1.0 ]nnane (Reaction A) A solution ofsodium a'lcoholate, prepared from 9.2 parts of sodium metal and 157parts of ethanol, was treated with 65.5 parts of 2,4-dichlorophenol. Tothis solution at reflux, 32.1 parts of 1,4,5,6,7,7-hexachloro-2-hydroxymethylbicyclo(2.2.1)-5-heptene in 78.5 parts by weight of ethanolwas added portionwise over 0.5 hour. The suspension was stirred atreflux for 3.0 hours. The reaction mixture was evaporated to one-thirdof its volume and the residue added to a large excess of water. The oilthat separated, crystallized on standing to yield 32 parts of solidwhich recrystallized from hexane to yield 15 parts of solid productmelting at 109 to 129 degrees centigrade. The solid was treated wtihdilute aqueous caustic, then recrystallized from heptane to yield asolid having a melting point of 136 to 138 degrees centigrade. Theproduct analysis was:

Calculated for C H Cl O C, 36.76; H, 1.98; Cl, 54.26. Found: C, 37.00;H, 2.0; Cl, 54.7.

Example 3.Preparation of 4-ethylmercapto-5,6,7,7,8pentachloro-3-oxatricyclo [4.2. 1 .0 nonane (Reaction A) Into 78.5 partsby weight of ethanol were slowly mixed 4.6 parts of sodium metal in areaction vessel. Then, 12.4 parts of ethyl mercaptan were added to thevessel, and thereafter 16.5 parts of1,4,5,6,7,7-hexachloro-2-hydroxymethyllbicyclo(2.2.1)-5-heptenedissolved in 78.5 parts by weight of ethanol were added over a period often minutes at 69 degrees centigrade. The reaction mixture was refluxedat 80 degrees centigrade for two hours. Then, the reaction mixture wascooled, water was added, and the product was acidified with hydrochloricacid to neutralize it. The resulting mixture Was extracted three timeswith diethyl ether, and was distilled to remove the solvent. Theresulting brown oil product (17.8 parts by Weight) was fractionated. Thefraction boiling at 138 to 144 degrees centigrade and 0.2 mm. was ayellow oil (8 parts) having the following analysis:

Calculated for C H Cl SO: C, 33.69; H, 3.11; Cl, 49.8; S, 8.98. Found:C, 33.61; H, 3.05; Cl, 49.9; S, 9.13.

Suitable alcohols or like media for use in forming an alkoxide, or asthe alcoholic medium for Reaction A,

are those having the formula R ZH, wherein Z is selected from the groupconsisting of oxygen and sulfur, and R is selected from the groupconsisting of hydrocarbyl, halogen-substituted aryl, hydroxy-substitutedhydrocarbyl, mercapto-substituted hydrocarbyl,hydrocarbyloxy-substituted hydrocarbyl, and hydrocarbylthio-substitutedhydrocarbyl. The hydrocarbyl, and halogen-substituted aryl groups arethe same as those described hereinbefore in connection with R R R and RThe products of Reaction A can be reacted with halogens and halogenhalides to produce compounds wherein the hydrocarbyl, e.g., alkyl,cycloalkyl, alkenyl and aryl substituents as represented by X X X X R RR R and R are converted to the corresponding halogen-substitutedradicals as represented by X X X X R R R R and R respectively, Rrepresents the same radicals as R and, in addition, halogen-substitutedalkyl and halogen-substituted cycloalkyl. The halogensubstituted alkyl,alkenyl, cycloalkyl and aryl radicals are as described hereinbefore.

Example 4.Preparation of 4,5,6,7,7,8-hexachloro-3- oxatricyclo[4.2.1.0]nonane (Reaction B) 10 parts of4-methoxy-5,6,7,7,8-pentachloro-3-oxatricycl0[4.2.1.0 ]nonane were mixedwith 158.4 parts by weight of carbon tetrachloride. Gaseous chlorine wasintroduced into the reaction mixture in the presence of a mercury vaporlight at a temperature of 78 to 80 degrees centigrade for 0.66 hour.When 34 milliequivalents of chloride ion had been collected overheadfrom the reaction mixture, a sample of the product was removed from thereactor, the solvent was evaporated and the resulting colorless syrupwas found to have a chlorine content of 58.4 percent. The remainder ofthe reaction mixture was chlorinated further until 0.0145 mole ofchlorine ion had been added. The resulting product was evaporated toremove the solvent, thus producing a light brown cloudy syrup. Infraredanalysis showed that the product was free of carbonyl group. The productcontained 68.5 percent chlorine. The chlorine content of the desiredproduct is calculated to be 68.4 percent.

Example 5.Preparation of 4-hydroxy-5,6,7,7,8-pentachloro-3-oxatricyclo[4.2.1.0 ]nonane (Reaction C) A suspension of 30 parts of4-etl1oxy-5,6,7,7,8-pentachloro-3-oxatricyclo[4.2.1.0 ]nonane in 92parts by weight of concentrated sulfuric acid was warmed to 88 todegrees centigrade with stirring and was held for 0.75 hour. The hotacid solution was poured into 700 parts of ice and water, and theresulting suspension was warmed to 80 degrees centigrade, then cooledand filtered. Then, 13 parts of solid product were recrystallized frombenzene several times to yield 7 parts of White crystals having amelting point of 231 to 232 degrees centigrade. Infrared analysis of theproduct indicated the presence of hydroxyl group, absence of carbonylgroup. Elemental analysis showed:

Calculated for C H Cl O C, 30.75; H, 2.24; Cl, 56.70. Found: C, 30.96;H, 2.20; Cl, 56.90.

Using the method of Example 5, the compound 9- chloromethyl 4 hydroxy5,6,7,7,8 pentachloro 3- oxatricyc1o[4.2.1.0 ]nonane is prepared from9-chloromethyl 4 ethoxy 5,6,7,7,8 pentachloro 3 oxatricyclo [4.2.1.0]nonane. The latter compound is prepared by reacting 4-ethoxy 9hydroxymethyl-S,6,7,7,8-pentachloro-3-oxatricyclo[4.2.1.0 ]nonane withphosphorus pentachloride at elevated temperature until hydrogen chlorideevolution ceases. The 9-hydroxymethyl derivative is prepared from1,4,5,6,7,7hexachloro 2,3 di(hydroxymethyl)bicyclo(2.2.1)-5-heptene bythe method of Example 1.

Example 6.-Preparation of 2-keto-5,6-bis(chloromethyl) 1,3,4,7,7pentachlorobicyclo(2.2.l)heptane (Reaction D) A mixture of 100 parts of9-chloromethyl-4-hydroxy- 5,6,7,7,8 pentachloro 3 oxatricyclo [4.2.1.0]nonane and 74 parts of phosphorus pentachloride was heated slowly tothe reflux temperature. An exothermic reaction took place, accompaniedby evolution of hydrogen chloride. The reaction mixture was refluxed at136 degrees centigrade for 1.5 hours. The resulting reaction product waspoured into water and washed thoroughly and then extracted with hexane.The reaction product was dried in contact with magnesium sulfate andthen the hexane solvent was distilled off. The product distilled at atemperature of 140 to 144 degrees centigrade and 1 mm. mercury. Infraredanalysis of the product indicated the presence of the carbonyl group.Chemical analysis gave the following results:

Calculated for C H CI O: C, 28.57; H, 1.60; Cl, 65.6. Found: C, 28.32;H, 1.66; Cl, 68.2.

Example 7.Preparation of4-cyano-5,6,7,7,8-pentachloro-3-oxatricyclo[4.2.1.0 ]nonane (Reaction E)A solution containing 132 parts of 2-keto-5,6-bis(chloromethyl)1,3,4,7,7 pentachlorobicyclo(2.2.1)heptane in 785 parts by weight ofethanol and 30 parts by weight of water was treated with 52 parts ofpotassium cyanide. The solution was stirred at reflux for 2.0 hours. Theresulting dark suspension was acidified with dilute sulfuric acid andthen evaporated to near dryness. The residue was poured into water andthe brown solid collected on a filter. The solid was dissolved inhexane, dried over magnesium sulfate (anhydrous), and filtered. Theexcess hexane was removed, and crystals separated upon chilling thesolution. Sixty parts of product were recovered having a melting pointof 226 to 231 degrees centigrade. Recrystallization raised the meltingpoint to 235 to 236 degrees centigrade.

Elemental analysis of the product gave the following results:

Calculated for C H ONCl C, 33.63; H, 1.88; N, 4.36; Cl, 55.16. Found: C,33.7; H, 2.02; N, 4.28; Cl, 54.98. Example 8.Preparation of4-carboxy-5,6,7,7,8-pentachloro-3-oxatricyclo-[4.2.1.0 ]nonane (ReactionF) To a mixture of 552 parts by weight of sulfuric acid, 100 parts byweight of water and 1,050 parts by weight of glacial acetic acid wereadded 80 parts of 4-cyano-5,6,7,7, 8-pentachloro-3-oxatricyclo[4.2.l.0]nonane. The mixture was stirred and heated to 127 degrees centigrade atwhich temperature slight refluxing occurred. Refiuxing was continued for14 hours, and the reaction mixture was added to 5,000 parts by weight ofwater. The solid product was filtered from the mixture, washed withwater and dried. The resulting product was 60 parts of white solidhaving a melting point of 279 to 281 degrees centigrade. The product hada chlorine content of 51.8 percent. The calculated chlorine content forC H Cl NO- is 52.1 percent. The acid number of the product correspondedclosely to the theoretical value:

Calculated neutralization equivalent: 340. Found: 339.

Examples 9 to 11.Fungicidal activity Finely divided aqueous dispersionof various compounds of the invention were prepared by dissolving themin a minimum quantity of acetone and pouring the solutions into waterwith vigorous agitation, to obtain dispersions containing 400 parts ofthe chemical per million parts of water (i.e., 0.04 percent). Thesedispersions were quickly sprayed onto tomato plants which had beeninoculated with spores of Alternaria solani, the causative organism ofearly blight disease of tomatoes. Three days later, when similarlyinoculated but unsprayed plants were severely diseased, as shown by leafnecrosis, the treated plants showed the following degree of diseasecontrol:

*Scale: 0=no control; 1=slight control; 2=substantial, economicallyuseful control; 3=essentially complete control of leaf necrosis.

Example 12.Bacteriostatic activity The incorporation of 255 parts permillion of the compound of the formula into nutrient agar which was theninoculated with Staphylococcus aureus, strongly retarded growth of thebacterial colonies on the agar.

Example l3.Herbicidal activity The application of four pounds per acreof the compound of the formula in finely divided form onto a healthystand of millet resulted in percent kill of the millet within one week.

Example 14.-Miticidal activity Bean plants heavily infested with redspider mites were sprayed with an aqueous dispersion of the compound ofthe formula cc1 =cct m H c H o at the rate of 1,000 parts of thecompound per million parts of water. Within 48 hours, essentially all ofthe mites were dead.

was dispersed in finely divided state in water at concentrations of 500and 1,000 parts of compound per million parts of water. The suspensionwas sprayed onto the leaves of bean plants. After the water evaporated,the larvae of Southern Army Worm was applied to the leaves. The leaveswere observed 24 hours later, and it was found that percent kill hadresulted.

Example l6.--Plant growth regulation The compound of the formula wasapplied at a rate of 8 pounds of compound per acre to soil in whichbeans had been planted, but prior to emergence of the bean plants.Another plot of soil in which beans had been planted at the same time asin the test plot was left untreated. After a period of two weeks, thebean plants in the untreated soil had grown to normal size. In contrast,the plants in the test plot were extremely stunted, but no othermalformation or toxic effect was observed.

In the foregoing manner, the utility of the compound of the inventionwas demonstrated as a plant growth regulator. This property is importantin the cultivation of ornamental plants, as well as in cultivation offruit trees where it is desirable to retard the tree growth. Thecultivation of shorter fruit trees also facilitates the picking of thecrop.

In the foregoing examples, the components have been named in accordancewith the system of nomenclature employed by Chemical Abstracts, and withthe provision that the compounds have the following structural formula Ia o 2 3 wherein the numerals indicate the position of substituentsattached to the tricyclic nucleus. Thus, the compound prepared inExample 1 has been named 4-ethoxy-5,6,7,7,8-pentachloro-3-oxatricyclo[4.2.1.0 ]nonane. Attachment of the oxygen to adifferent position on the initial bicyclic structure to provide thefollowing structural formula requires renumbering some of the positionsof the tricyclic structure, as indicated by the numerals. Under thesecircumstances, the compound produced in Exampl 1 is named4-ethoxy-5,6,6,7,9 pent-achlor-3-oxatricyclo[3.2. 1 ]nonane.

As shown in the preceding examples, the compounds of the invention areuseful in a variety of applications requiring biological activity. Suchactivity includes utility as fungicides, insecticides, bactericides,herbicides, and as plant growth regulators.

When compounds of the invention are utilized in controlling bacteria,the compound is brought into contact with the bacteria to be controlledin an amount sufiicient to provide the desired control of the bacteria,e.g., a bactericidal amount. Typically, the compound is applied at arate within the range of about to 25 grams per square meter of thesurface to be treated. However, either greater or lesser applicationrates can be used depending on the conditions that exist and the extentof control required. The compound of the invention can be applied to thearea in which bacteria is to be controlled as an aqueous suspension orsolution containing the compound in an amount in the range of 5 to about50 percent by weight of the aqueous composition.

The herbicidal compounds of the invention can be used alone or as partof liquid or solid formulations of various types. Thus, the compoundscan be formulated as liquids by diluting, dispersing, dissolving oremulsifying with a surface active adjuvant in organic solvents such :aspetroleum hydrocarbons, alcohols, ketones, esters, and the like. Thecompounds can be made into solid formulations of powders, dusts,wettable dusts, granules and pellets, using solid diluents such as talc,clay, flour, starch, mica, limes, carbonates and phosphates. Generally,the proportions of either the solvent medium or solid carrier toherbicidally active material is in the range of 1:1 to 1,00021,preferably 3:1 to 200: 1. Rates of application vary according to thedegrees of resistance of the plants to be controlled, the soil type andclimatic conditions, but, in general, the rates of application are atleast one quarter of a pound of herbicides per acre up to 400 pounds peracre, preferably 0.5 to 50 pounds per acre, but in any event, in anamount suificient to provide the desired control, e.g., a herbicidalamount.

When desired for plant growth regulation, the compounds of the inventionare similarly formulated as liquid or solid formulations. However, thecompounds are used in an amount to provide the desired amount of growthregulation.

When compounds of the invention are utilized in the control of insectsand other invertebrate pests, including mites, and many others, thecompound is brought into contact with the pest to be controlled in anamount sufiicient to provide the desired control, e.g., a pesticidalamount, or an insecticidal amount, and the like. Effective insecticidalconcentrations are in the range from about 0.01 pound per acre to about20 pounds per acre. In most c-rop applications, rates of 0.05 to 5pounds per acre are employed. Lower rates are used on very susceptiblespecies, while higher rates are used on extremely resistant species. Theinsecticidal compounds can be used in combination with a class ofpotentiators or synergists known in the insecticidal art as knockdownagents. Other adjuvants useful with the compounds of the inventioninclude odorants, colorants, stabilizers, and extending agents. Thecomposition can be formulated as solids or liquids using solid or liquidsolvent vehicles, carriers or extenders. The compounds can [also becombined with other pesticidally active compounds.

When compounds of the invention are applied as fungicides, the compoundis employed in an amount sufiicient to provide the desired control ofthe fungus, e.g., a fungicidal amount. The compounds are generally usedat rates ranging from 0.05 to pounds per acre. Very low rates, 0.05 to 1pound per acre are suflicient when the compounds are utilized as seedtreatment chemicals. Higher rates, 0.1 to 20 pounds per acre, are usedwhen a crop is treated in the field, such as in the application ofsprays, dusts and granules. Rates up to 100 pounds per acre are utilizedwhen it is necessary to treat an entire mass of soil to a considerabledepth in heavily infested fields.

The compounds can be used with other active agents such as insecticides,herbicides, fertilizers, plant growth regulators, and other fungicides.The compounds can be used in the pure state or with suitable adjuvants,such as solvents, solid carriers, surfactants, synergists, colorants andodorants.

While this invention has been described with reference to certainspecific embodiments, it will be recognized by those skilled in the artthat many variations are possible without departing from the spirit andscope of the invention.

What is claimed is:

1. A method for the control of plant growth, comprising applying to thelocus to be treated a herbicidal amount of a compound of the formula (2)R is selected from the group consisting of hydrocarbyl,halogen-substituted hydrocarbyl, hydroXy-substituted hydrocarbyl,mercapto-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, and hydrocarbylthio-substituted hydrocarbyl; wherein alkylhas 1 to 18 carbon atoms, alkoxy has 1 to 18 carbon atoms, hydrocarbylhas 1 to 18 carbon atoms, cycloalkyl H i R has 3 to 12 carbon atoms,hydrocarbyloxy has X5 1 to 18 carbon atoms and hydrocarbylthio has 1 to18 carbon atoms.

Y v 3. The process of claim 2, wherein R is hydrogen.

' 1, 4. The process of claim 1, wherein: 0 3 (a) X X X X and X arechlorine; and

| (b) Y is chlorine. 5. The process of claim 1, wherein:

wherein X and X are independently selected from the group consisting ofhydrogen, halogen, alkyl, alkenyl, halogenated alkyl and halogenatedalkenyl;

X and X are independently selected from the group consisting ofhydrogen, halogen, alkoxy, alkyl, alkenyl, halogenated alkyl, andhalogenated alkenyl, at least two of X X X and X being halogen;

X is selected from the group consisting of hydrogen,

halogen and alkoxy;

Y is a nucleophilic radical;

R and R are independently selected from the group consisting ofhydrogen, hydrocarbyl, halogen-s'ubsti- 30 tuted hydrocarbyl, andcarboxy;

R and R are independently selected from the group consisting ofhydrogen, hydrocarbyl, halogen-substituted hydrocarbyl,hydroxy-substituted alkyl, alkoxystituted alkyl, and hydroxy-substitutedalkoxyalkyl;

(a) X X X X and X are chlorine; and (b) Y is CEN. 6. The process ofclaim 1, wherein: (a) X X X X and X are chlorine; and

(b) Y is COOH. 7. The process of claim- 1, wherein: (a) X X X X and Xare chlorine; and (b) R R R and R are hydrogen; and (0) Y isethylmercapto.

8. The process of claim 1, wherein: (a) X X X X and X are chorine; and(b) R R R and R are hydrogen; and (c) Y is chloro. 9. The process ofclaim 1, wherein: (a) X X X X and X are chlorine; and (b) R R R and Rare hydrogen; and (c) Y is hydroxy. 10. The process of claim 1, wherein:

and (a) X X X X and X are chlorine; and

R and R are cycloalkyl when R and R join to form a ring; provided thatat least one of R and R can be hydroxy-substituted alkyl when Y is oneof halogen, hydroxy, hydrocarbyloxy, mercapto, substituted 4ohydrocarbyloxy and substituted hydrocarbylmercapto; wherein alkyl has 1to 18 carbon atoms, alkenyl has 1 to 18 carbon atoms, alkoxy has 1 to 18carbon atoms, hydrocarbyl has 1 to 18 carbon atoms, cycloalkyl has 3 to12 carbon atoms, hydrocarbyloxy has (b) R R R and R are hydrogen; and(c) Y is carboxy.

11. The process of claim 1, wherein:

(a) X X X X and X are chlorine; and (b) R R R and R are hydrogen; and(c) Y is 2',4-dichorophenoxy.

References Cited UNITED STATES PATENTS 2,841,485 7/1958 Johnson et a1.71 2.5 XR 1 to 18 carbon atoms, hydrocarbylmercapto has 1 93 7 5 19Gearing et 1 71 2 5 XR to 18 carbon atoms and hydrocarbylthio has 1 to 3038,794 6/1962 Geary t 1, 71-25 18 carbon atoms. 3,298,815 1/ 1967 Mark712.5

2. The process of claim 1, wherein: (a) X X X X and X are chlorine; (b)Y is a nucleophilic radical of the formula R 2 wherein:

(1) Z is selected from the group consisting of oxygen and sulfur; and

LEWIS GoTTs, Primary Examiner.

G. HOLLRAH, Assistant Examiner.

US. Cl. X.R.

2%? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3+19.380 Da December 31 I968 Inveutofls) Paul E. Hoch and George B.Stratton It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

C01 umn 2, 1 ine 5, after "greater" the word should be corrected to readas---part1'cu1arity---. Column 2, line 58, the word after the secondoccurrence of "to" should be corrected to read as---perha1ogenation---.Column 8, Iine 35, the formula should be corrected to read as SIGNED ANDSEALED FEB 241970 WILL! I. SOHUYLER, JR- Edwml Dominican of PatentsAttesting Officer

